The present invention relates to solid, hydrocarbon insoluble, mixed catalyst compositions useful in the heterogeneously catalyzed polymerization of olefins to high molecular weight olefin homopolymers and copolymers, especially polyethylene, polypropylene, and ethylene/propylene copolymers.
It is previously known to prepare solid catalyst compositions comprising a conventional Ziegler-Natta supported transition metal composition and a homogeneous catalyst composition such as a metallocene. Examples include U.S. Pat. Nos. 5,747,405, 5,539,076, 5,395,810, 5,266,544, 5,183,867, 4,659,685, EP-A's 676,418, 717,755, 705,848, 747,402, and WO's 98/02245, 96/13532, and 95/13871. Suitable supports included silica, alumina, and magnesium-dichloride.
Coordination complexes of Group 4 metals and unsaturated compounds such as cyclopentadiene or heteroallyl compounds are described in U.S. Pat. No. 5,527,752. In addition, U.S. Pat. No. 5,387,567 discloses a method of treating soluble zirconium complexes with cyclopentadiene to produce a homogeneous catalyst component for use in solution polymerizations. Solid, hydrocarbon insoluble catalyst compositions comprising the reaction product of a cyclopentadiene and a magnesium alkoxide based Ziegler/Natta composition are disclosed in WO01/48036, WO01/48037 and WO01/48038.